New chemical compounds



United States Patent 1 2,880,239 NEW CHEMICAL COMPOUNDS Peter William Brett Semmens and James Denis Summers- Smith, Norton-on-Tees, England, assignors to Imperial Chemical Industries Limited, London, England, a corr t n e Grea r t Ne D i App eti n January 30, 956

Serial No. 562,039

Claims priority, application Great Britain February 23, 1955 2 Claims, (Clztowssv- This huesea e tes te- FhQEliQQ! eempeunds suitable for use as boundary lubricants. The invention also relates to methods of preparing these compounds, n t omp si ions Qf ma ter i h een hem an W h a s t b fer tee as b nda y lu nts.

nd r u rieants e iee i n l tin ee e tieu rl me l surteees. whieh are id n lafive me enether mi der b aade y eend s,

W ha e 9 24. the! uate na y ammon pxr aheephate salts as hereinafter defined, which are new compounds, may be prepared as hereinafter described, and

may be used either alone or in suitable compositions of matter to provide effective boundary lubricants.

According to the present invention, therefore, we provide quaternary ammonium pyrophosphate compounds as hereinafter defined, which are new chemical compounds, and which are suitable for use as boundary lubricants. Also according to the present invention, we provide processes for the production of quaternary ammonium pyrophosphate compounds as hereinafter defined. The present invention also provides compositions of matter suitable for use as boundary lubricants which comprise one or more quaternary ammonium pyrophosphate compounds as hereinafter defined and one or more suitable liquid or solid vehicles in which the pyrophos phate compound or compounds may be dissolved or dispersed.

The quaternary ammonium pyrophosphate compounds of the present invention are salts in which two or four hydrogen atoms of pyrophosphoric acid are replaced by quaternary ammonium groups, the nitrogen atom of each of which is attached to at least one radical containing at least one alkyl group having six or more carbon atoms.

Suitable quaternary ammonium groups include cetyl trimethyl ammonium, didecyl dimethyl ammonium, cetyl pyridinium, tetradecyl pyridinium, lauryl benzyl dimethyl ammonium, octyl phenoxy-ethyl benzyl diethyl ammonium, di-octyl dimethyl ammonium, stearamido benzyl dimethyl ammonium.

Suitable liquid vehicles in which the pyrophosphate compounds of this invention may be dissolved or dispersed to provide boundary lubricants include hydrocarbons, mineral oils, vegetable oils such as castor oil, siloxane oils, aliphatic esters and alkylene glycols. Suitable solid vehicles include hydrocarbons such as petroleum jelly, animal fats, vegetable and mineral grease-like substances, solid siloxane compounds, fatty acids and soaps and esters thereof. These vehicles may be used singly, or in combination with one another, and may be mixed with one or more pyrophosphate compounds.

The pyrophosphate compounds of this invention are in general water-soluble grease-like solids. The nature of the compositions of matter of this invention may be varied by selection of the proportion of pyrophosphate compound or compounds chosen, and by selection of the vehicle or vehicles. If, for example, a boundary lubrie f compa a i o vieeesi y s required, h a sui ble liqu d veh ele is haser. and sme l p opo t on. o p rephee hete is dissolve d sper ed h i I e prop ien f yropho pha compou d a l quid e i in ased hen the is os ty f th re tan et ue is a s aere s dn. the e he ha a comu sit en h in a hig vissesity but. c n aining only sma l p e ertie q pyrephesphate eeinpeund may e obtained by selecting a. suitable solid or semi-solid vehicle.

Th prepar on at pyreplresphe e empeunds of t inv stin s tr ated in the te le ius examp s:

EXAMPLE 1 2.0 1 em ot a sui ab e ien esehanse r in h a hat sold unde t e Br ish. regis ered trad mark "Amb rlite,"- IRA.-. 9 (polysty ene qu packed in a column 1 inch in diameter and 18 inches o g were act vated by eentaet with. 2 t es. e a 5 by weight queo s. sel ien o sta m h drexid and Washed t water unu. t e washings, whi h were jected, gave a pH ofi i=8.

Qm1 a .0% by wei ht a ueaus alutieu c cetyl trimet yl mmonium bremide were reeee edly passe through the column until no bromide ion was detected in the collected drainings, which thus contained cetyl trimethyl ammonium hydroxide. The complete removal of bromide ion from the drainings was facilitated by reactivating the column in the manner described previously, and then continuing the passage of the collected drainings containing cetyl trimethyl ammonium hydroxide.

An aqueous solution of phosphoric oxide (P 0 was prepared equivalent to a N solution of pyrophosphoric acid. Approximately 57 mls. of this solution were needed to adjust 225 mls. of the collected drainings from the column to a pH of 4.5. The resulting solution was evaporated under vacuum and the product was finally dried over phosphoric oxide in a vacuum desiccator, yielding 5.8 gms. of a whitish-yellow grease having the following analysis:

This compared with a theoretical analysis for di(cetyl trimethyl ammonium)dihydrogen pyrophosphate of:

EXAMPLE 2 250 mls. of a solution of cetyl trimethyl ammonium hydroxide, prepared according to the method in Example 1, were adjusted to a pH of 8.5 by the addition of a solution of phosphoric oxide (P 0 prepared according to Example 1. Two liquid layers formed, and the upper layer after separation was dried over phosphoric oxide (P 0 in a vacuum desiccator to yield 9.5 gms. of a yellow grease having the following analysis:

This compared with a theoretical analysis for tetra- (cetyl trimethyl ammonium) pyrophosphate of EXAMPLE 3 This example illustrates an alternative method of preparing tetra-pyrophosphate salts according to this invention.

200 gms. of the ion-exchange resin sold under the British registered trademark Amberlite IRA-400 (polystyrene quaternary ammonium type) in a column 1 inch in diameter and 18 inches long were activated by contact with an aqueous solution containing 5% by weight hydroxide, prepared according to the method given in 5 Example 1, were adjusted to a pH of 7.0 with an aqueous N solution of sulphuric acid. Theres'ult'ant solu-' tion was then passed repeatedly down the column of ion exchange resin which had been activated with sodium pyrophosphate solution. The passage of liquid was con tinued until the collection drainings were free from sulphate ion. The collected drainings were then evaporated under reduced pressure and finally dried over phosphoric oxide in a vacuum desiccator, yielding 0.7 gms. of a waxy solid.

The pyropho sphate compounds as such prepared in the foregoing examples were found to be efiectivelubricantsbetween pairs of mild steel and stainless steel surfaces sliding relative to one another under boundary conditions. The value of this efiect is particularly important in the case of austenitic stainless steel surfaces, as it is well known to be very difiicult to lubricate such surfaces under boundary conditions.

The following table gives the coefficient of friction between austenitic stainless steel surfaces sliding at a speed of 0.08 cm. per second relative to one another, and lubricated with the pyrophosphate compounds of the fore-. going examples at temperatures of 20-200 C. Comparable results using petroleum jelly alone are also given.

Table Ooefi'iclent of friction at 0.08 ems/second Lubricant 0. O. O. O. O. O C. O.

D.O.D.H- v0.09 0.10 0.05 0.05 0.05 0.05 0.05 0.03 T.C.(2) 0.07 0.07 0.07 0.07 0.00 0.05 0. 06 0.05 T.O.(3 0.15 0. 14 0.14 0.14 0.13 0.13 0.12 0.13 Petroleum Jel1y 0.13 0. 17 0.18 0.18 0. 20 0.20 0.21 0. 1D

'D.O.D.H.Di(cetyl trimethyl ammonium) dlhydrogen pyrophosphate.

T.O.(2)Tetra(cetyl trimethyl ammonium) pyrophosphate prepared according to Example 2.

T.C.(3)-Tetra(cetyl trimethyl ammonium) pyrophosphate prepared according to Example 3. 1

We claim: 1. Di(cetyl trimethyl ammonium) dihydrogen pyrophosphate.

2. Tetra(cetyl trimethyl ammonium) pyrophosphate.

References Cited in the file of this patent UNITED STATES PATENTS 

1. DI-(CETHYL TRIMETHYL AMMONIUM) DIHYDROGEN PYROPHOSPHATE. 